Force Field Development from Periodic Density Functional Theory Calculations for Gas Separation Applications Using Metal–Organic Frameworks

Mercado, Rocío; Vlaisavljevich, Bess; Lin, Lu; Lee, Kyuho; Lee, Yongjin; Mason, Jarad A.; Xiao, Dianne J.; Gonzalez, Miguel I.; Kapelewski, Matthew T.; Neaton, Jeffrey B.; Smit, Berend

doi:10.1021/acs.jpcc.6b03393

Cited by 101 publications

(180 citation statements)

References 65 publications

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“…Buckingham parameters modelling the interactions of CO 2 with the framework were adapted directly from the work of Mercado et al 43,. the TraPPE force field was used to model N 2 –N 2 interactions44 and the EPM2 force field was used to model CO 2 –CO 2 interactions45.…”

Section: Methodsmentioning

confidence: 99%

Adsorbate-induced lattice deformation in IRMOF-74 series

et al. 2017

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IRMOF-74 analogues are among the most widely studied metal-organic frameworks (MOFs) for adsorption applications because of their one-dimensional channels and high metal density. Most studies involving the IRMOF-74 series assume that the crystal lattice is rigid. This assumption guides the interpretation of experimental data, as changes in the crystal symmetry have so far been ignored as a possibility in the literature. Here, we report a deformation pattern, induced by the adsorption of argon, for IRMOF-74-V. This work has two main implications. First, we use molecular simulations to demonstrate that the IRMOF-74 series undergoes a deformation that is similar to the mechanism behind breathing MOFs, but is unique because the deformation pattern extends beyond a single unit cell of the original structure. Second, we provide an alternative interpretation of experimental small-angle X-ray scattering profiles of these systems, which changes how we view the fundamentals of adsorption in this MOF series.

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Section: Methodsmentioning

confidence: 99%

Adsorbate-induced lattice deformation in IRMOF-74 series

et al. 2017

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“…The previous observations imply that the rigid framework approach is not valid for this material, despite its application in earlier studies. 16,19,41 An extension of the approach followed here using a hybrid MC/MD approach (where the MD part allows changes in framework geometry due to the presence of guest molecules) might be interesting for future computational studies but is out of the scope of this work.…”

Section: Resultsmentioning

confidence: 99%

Ab Initio Evaluation of Henry Coefficients Using Importance Sampling

Vandenbrande

Waroquier

Speybroeck

et al. 2018

J. Chem. Theory Comput.

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We present a new algorithm that allows for an efficient evaluation of the Henry coefficient of a guest molecule inside a porous material, which permits to use ab initio energy calculations. The Widom insertion method, which is currently used to compute these Henry coefficients, typically requires millions of energy evaluations. Our new methodology reduces this number by more than 1 order of magnitude, enabling the use of an ab initio potential energy surface. The methodology we propose is reminiscent of the well-known importance sampling technique which is frequently used in Monte Carlo integrations. First, a conventional Widom insertion simulation is performed using a force field. In the second step, the Widom results are used to select a limited number of configurations and only for these configurations the ab initio evaluation of the energy is required. Finally, by appropriately reweighting the latter energies, an accurate estimation of the ab initio Henry coefficient is possible at a moderate computational cost. We apply our methodology to the adsorption of CO2 in Mg-MOF-74, a prototypical case where interactions of a polar guest molecule with unsaturated metal sites dominate the adsorption mechanism. In this case generic force fields such as UFF or Dreiding are inappropriate and the use of ab initio methods is indispensable. In a second case study, we compute Henry coefficients of methane in UiO-66 using different levels of theory. We pay particular attention to the influence of the dispersion corrections and the role of many-body effects. For the final example, we qualitatively investigate adsorption features for a series of functionalized UiO-66 frameworks. Overall the cases we present show that accurate computations of Henry coefficients is extremely challenging, as different levels of theory provide strongly varying results. At the same time ab initio calculations have added value compared to force fields, as they provide a physically more sound description of the adsorption mechanism and in some cases clearly improve correspondence with experiment.

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“…39 The parametrization was peformed by calculating DFT single-point energies along the path of minimum repulsion between unique guest–host pairwise types to accurately capture the repulsive behavior between the guest and the excess electon density at the open metal sites. We adopt this force field parametrization for studying the adsorption properties of CO 2 and H 2 O in DHFUMA and refer the reader to this publication for specific details and the parameters themselves.…”

Section: Methodsmentioning

confidence: 99%

Rational Design of a Low-Cost, High-Performance Metal–Organic Framework for Hydrogen Storage and Carbon Capture

et al. 2017

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We present the in silico design of a MOF-74 analogue, hereon known as M2(DHFUMA) [M = Mg, Fe, Co, Ni, Zn], with enhanced small-molecule adsorption properties over the original M2(DOBDC) series. Constructed from 2,3-dihydroxyfumarate (DHFUMA), an aliphatic ligand which is smaller than the aromatic 2,5-dioxidobenzene-1,4-dicarboxylate (DOBDC), the M2(DHFUMA) framework has a reduced channel diameter, resulting in higher volumetric density of open metal sites and significantly improved volumetric hydrogen (H2) storage potential. Furthermore, the reduced distance between two adjacent open metal sites in the pore channel leads to a CO2 binding mode of one molecule per two adjacent metals with markedly stronger binding energetics. Through dispersion-corrected density functional theory (DFT) calculations of guest–framework interactions and classical simulation of the adsorption behavior of binary CO2:H2O mixtures, we theoretically predict the M2(DHFUMA) series as an improved alternative for carbon capture over the M2(DOBDC) series when adsorbing from wet flue gas streams. The improved CO2 uptake and humidity tolerance in our simulations is tunable based upon metal selection and adsorption temperature which, combined with the significantly reduced ligand expense, elevates this material’s potential for CO2 capture and H2 storage. The dynamical and elastic stabilities of Mg2(DHFUMA) were verified by hybrid DFT calculations, demonstrating its significant potential for experimental synthesis.

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Force Field Development from Periodic Density Functional Theory Calculations for Gas Separation Applications Using Metal–Organic Frameworks

Cited by 101 publications

References 65 publications

Adsorbate-induced lattice deformation in IRMOF-74 series

Adsorbate-induced lattice deformation in IRMOF-74 series

Ab Initio Evaluation of Henry Coefficients Using Importance Sampling

Rational Design of a Low-Cost, High-Performance Metal–Organic Framework for Hydrogen Storage and Carbon Capture

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